Keto acid containing compositions

ABSTRACT

Improved surfactant and shampoo compositions which have improved solubility and foaming characteristics, which compositions comprise a keto acid in combination with surfactants, brighteners, conditioners, and the like.

United States Patent 1 Corey 1 Feb. 19, 1974 KETO ACID CONTAININGCOMPOSITIONS [75] Inventor: Garland George Corey, Milltown,

[73] Assignee: Colgate-Palmolive C0., New York,

[22] Filed: Sept. 3, 1971 21 Appl. No.: 177,855

Related US. Application Data [63] Continuation of Set. No. 835,256, June20, 1969,

abandoned.

[52] US. Cl 252/89, 252/132, 252/D1G. 13, 424/70 [51] Int. Cl Clld 3/20[58] Field of Search. 252/89, DlG. 13, 132; 424/70; 260/526 R PrimaryExaminer-William E. Schulz [5 7 ABSTRACT Improved surfactant and shampoocompositions which have improved solubility and foaming characteristics,which compositions comprise a keto acid in combination with surfactants,brighteners, conditioners, and the like.

8 Claims, N0 Drawings KETO ACID CONTAINING COMPOSITIONS This is acontinuation of application Ser. No. 835,256 filed June 20, 1969 nowabandoned.

The instant invention is directed to novel surfactant and shampoocompositions. In particular, the instant invention is directed tosurfactant and shampoo compositions which contain keto acid.

There are numerous types of shampoos and surfactant compositions on themarket at present. Many of these compositions are based on soapsalthough there are numerous compositions which contain syntheticdetergent preparations. Such detergent preparations contain primarilyorganic sulfates and sulfonates. These detergent compositions arefavored by many consumers because they do an extremely thorough cleaningjob and further do not leave dulling lime soaps on the hair when hardwater is employed.

Under the conditions of use the synthetic detergents are better cleanersin that they effectively remove excess oils from the hair. Furthermore,the hair is more easily washed with said detergents than with soapbecause the use of soap requires that it be removed as thoroughly aspossible from the hair by asubsequent prolonged rinsing treatment withwater, which may leave behind an undesirable degree of alkalinity on thescalp.

In connection with shampoo compositions it is noted that most users ofshampoos have definite requirements with respect to the performancecharacteristics of the products they use. A shampoo which merely cleansthe hair is not necessarily a satisfactory product; it is often saidthat a shampoo which cleans too well is unsatisfactory. In addition tocleaning adequately, the product must lather well during the shampooingoperations and must condition the hair, i.e., leave the hair in a soft,smooth, lustrous and easily manageable state. The sham poo must be mildand have sufficient resistance to hard water since hard water may causea reduction in lather and cleaning efficiency and may cause anundesirable film formation on the hair. The use of softened water orspecial rinses are not satisfactory solutions to hard water problems fora commercially acceptable shampoo.

The chief problem in formulating a shampoo which has the combination ofthe requisite properties is that a particular ingredient which willimpart to the shampoo one or perhaps several of the requisite propertiesin an outstanding manner will adversely affect one or more of theremaining properties. For example, soapbased shampoos, in soft water,have excellent cleaning, lathering and hair conditioning properties;however, any hardness in water adversely affects the latheringcharacteristics and leaves the well known undesirable hard water soapcurd. Sequestering and curd dispersing additives have improved soapshampoos to some extent but the majority of successful shampoos arebased on those non-soap synthetic detergents which lather and clean wellin hard or soft water. Such non-soap detergents, however, have theshortcoming of cleaning so well that the natural oil of the hair, whichnaturally conditions the hair, is removed leaving it harsh andunmanageable.

If the shampoo preparation is designed to preserve much of the naturaloil in the hair, the criticism can be voiced that it does an incompletecleaning job. Some shampoos attempt to solve this problem by using ahighly effective detergent with a hair conditioning agent which servesas a replacement for the oil removed from the hair. Examples of suchhair condioning agents are polyglycols, fatty acid esters of glycols,natural or synthetic waxes, and lanolin derivatives. Use of formulationscontaining excessive amounts of hair conditioning agents of the oilytype may cause the hair to have an unpleasant oily appearance and feel.Formulations containing certain hair conditioning agents suffer from theadditional difficulty that the oily material inhibits sudsing of theshampoo. Most people have come to expect copious lather from theirshampoo and are dissatisfied if it is not formed.

It is an object of this invention to provide a homogeneous shampoo whichproduces a copious lather, effectively cleans the hair, and leaves thehair, after drying, in a soft, lustrous, easily manageable condition.

It is another object of this invention to provide a shampoo which hasthe above characteristics in hard as well as soft water and which doesnot form an undesirable hard water precipitate.

It has been found that these and other objects of the instant inventioncan be obtained by providing a shampoo composition which includes a ketoacid in combination with other conventional shampoo ingredients. For thepurposes of the present invention, it is intended that the term ketoacid be generic to encompass not only ketone acids but aldehyde acids aswell, i.e., acids containing an oxo-carbonylic group. The keto acidsemployed is connection with the instant invention have the generalformula:

0 i R (CHmCOOI-I wherein R represents hydrogen or an alkyl such asmethyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, decyl,dodecyl, tetradecyl, hexadecyl, octadecyl, eicosyl, and the like, and nrepresents an integer of from O to 3. These keto acids are all wellknown in the art and may be prepared in a known manner. Suitable ketoacids include, but are not limited to, the following:

ll CH CI-I CH CH CH CCOOH C CI-ICH COOH if CH CH CHCH COOH CH ,cmcmcniincn cn coou cn,cn,cn cmcmiincncn cn coon o I-ICH CH CH COOH 0 lcmdncmcincmcoon CHQCHZCHCHZCHZCHZCOOH ll cH,cH,cn,ci-|cn,cr|,cn,cooii Inaddition to theessential keto acid one may employ in connection with theinstant shampoo composition any of the usual ampholytic surface activeagents or detergents. Among those which provide best results are thefatty imidazolines, such as l-coco-5-hydroxyethyl- S-carboxymethylimidazoline known as Miranol CM, and other similar products made byreacting monocarboxylic fatty acids having chain lengths of to 24 carbonatoms with diethylene triamine and with monohalo monocarboxylic fattyacids having from 2 to 6 carbon atoms, the fatty beta-alanines such asdodecyl beta-alanine sold under the name dodecyl Deriphat, the innersalt of Z-trimethylamino lauric acid sold under the name Product BDO,betaines such as N- dodecyl-N,N-dimethylaminoacetic acid sold under thename Quatronyx, etc. Mixtures of any two or more of the foregoing may beemployed.

In addition to' ampholytic detergents one may also employ nonionicsurface active agents or mixtures thereof. Among the useful nonionicsurface active agents are the the ethylene oxide ethers of alkyl phenolssuch as nonylphenol polyoxyethylene ether, the ethylene oxide ethers offatty alcohols. such as tridecyl alcohol polyoxyethylene ether, theethylene oxide ethers of alkyl mercaptans such as dodecyl mercaptanpolyoxyethylene thioether, the ethylene oxide esters of the fatty acidssuch as lauric ester of polyethylene glycol and lauric ester of methoxypolyethylene glycol, the ethylene oxide ethers of fatty acid amides, thecondensation products of ethylene oxide with partial fatty acid estersof sorbitol. such as the lauric ester of sorbitan polyethylene glycolether, and other similar materials.

In addition, one may also employ a wide variety of cationic surfaceactive agents including distearyl dimethyl ammonium chloride, stearyldimethylbenzyl ammonium chloride, coco dimethylbenzyl ammonium chloride,dicocodimethyl ammonium chloride, cetylpyridinium chloride,cetyltrimethyl ammonium bromide, the stearyl amine salts that aresoluble in water such as stearyl amine acetate and stearyl aminehydrochloride, stearyl dimethylamine hydrochloride, distearyl aminehydrochloride, octyl phenoxyethoxyethyl dimethylbenzyl ammoniumchloride, decyl pyridinium bromide, the pyridinium chloride derivativeof the acetylaminoethyl esters of lauric acid, lauryl trimethyl ammoniumchloride, decylamine acetate, lauryl dimethylbenzyl ammonium chloride,and the like. Mixtures of two or more cationic surface agents may beemployed if desired.

Still further, one may employ anionic surface active agents such as andincluding but not limited to the alkyl sulfates such as sodium laurylsulfate, the fatty taurides such as cocomethyl tauride and tallow methyltauride, the sulfated monoglycerides, the sulfonated monoglycerides, thealkyl aryl sulfonates, lauryl hydroxy ether lauryl propionate, coconutacid ester of sodium isethionate, dioctyl ester of sodium sulfosuccinicacid, N- octa decyl tetrasodium l,2-dicarboxyl ethylsulfosuccinate),,.ammonium salt of sulfate ester of an alkyl phenoxypolyoxyethylene ethanol, sodium salt of lauryl polyoxyethylene sulfate,sodium salt of tridecyLether polyoxyethylene sulfate, fatty acid amidopolyoxyethylene sulfate, and the like, as well as mixtures thereof.

In addition to the detergentand keto acid, the instant shampoocompositions also include a solvent such as water, alcohol, isopropanol,glycerine, and the like. Furthermore, any of the conventional additivessuch as preservatives, dyes, pearling agents, perfumes, thickeners,opacifiers andthe like may be included in accordance with conventionalcompounding practice. Fur thermore, one may also include UV absorbers,thickeners, formaldehyde and conditioners as are conventionally employedin shampoo compositions.

One may employ in connection with the compositions of the instantinvention from about 5 to about 40 percent detergent ingredient. Inaddition, with regard to the keto acids, from aboutO.5 percent to about10 percent by weight is employedin connection with the compositions. i

As previously noted, we have unexpectedly found that when one employsthe above-delineated keto acids in a surfactant composition, one obtainsan increase in the foaming properties thereof and furthermore, anunexpected improvement in the conditioning aspects of the shampoosystems. This phenomenon is particularly noted when the keto acids areemployed in connection with acidic systems, i.e., surfactantcompositions having a pH of from about 3 to about 7, whereupon, inaddition to the above aspects, the keto acids also serve to increase thesolubility of the detergent systems. i

The instant invention will now be further'explained by the followingexamples. It is noted that the instant invention is not deemed as beinglimited thereto.

EXAMPLE 1 A surfactant composition was prepared according to thefollowing formulation:

Triethanolamine lauryl sulfate Alcohol 5.5% Lauryl myristicdiethanolamide 5% Phosphoric acid 10% Water The pH of the above systemwas adjusted with sodium hydroxide to a pH of 5.5. 3 grams of theproduct was mixed with 50 grams of tap water in a 500 millilitergraduated cylinder. The cylinder was stoppered and inverted times andthe amount of foam was read in cc's. As a result of this experiment, itwas found that the sample had 250 ccs of foam.

EXAMPLE 2 EXAMPLE 3 The procedure of Example 1 was repeated with thecomposition of Example 1 with the exception that distilled water wasemployed instead of tap water. As a result of the experiment the samplewas found to produce 225 ccs of foam.

EXAMPLE 4 The procedure of Example 2 was repeated with the exceptionthat distilled water was employed instead of tap water. As a result ofthe experiment the sample was found to produce 275 ccs of foam.

EXAMPLE 5 A shampoo formulation was compounded according to thefollowing formula:

Triethanolamine lauryl sulfate l9% Alcohol 5.5% UV absorber 0.4% Methylcellulose 0.9% Lauryl myristic diethanolamide 5% Water to l00% Theprocedure of Example 1 was repeated and as a result the composition wasfound to produce 325 cos of foam.

EXAMPLE 6 The composition of Example 5 was prepared with the exceptionthat 5 percent acetoacetic ethylate was added thereto. As a result ofthe procedure of Example 5 the composition was found to produce 350 ccsof foam.

EXAMPLE 7 The composition of Example 2 was prepared, with the exceptionthat in lieu of 7.3 percent levulinic acid, 9% glyoxylic acid wasemployed. The procedure of Example 2 was repeated and the sample wasfound to produce 425 ccs of foam.

EXAMPLE 8 The procedure of Example 4 was repeated, with the exceptionthat 5 percent glyoxylic acid was employed instead of 7.3 percentlevulinic acid. As a result of the experiment, the sample was found toproduce 240 ccs of foam.

EXAMPLE 9 The procedure of Example 6 was repeated, with the exceptionthat 2 percent pyruvic acid was employed in lieu of 5 percentacetoethylate. As a result of the experiment, the composition was foundto produce 340 ccs of foam.

As will readily be noted from the above Examples, when one adds a ketoacid to a shampoo formulation, one obtains an unexpected increase in thefoaming action thereof. It is also to be noted that by employing a ketoacid in the shampoo compositions, one also obtains unexpectedconditioning, softening and cleaning characteristics from the resultingshampoo composition.

What is claimed is:

l. A detergent composition consisting essentially of from about 50 toabout 94.5 percent water, from about 5 to about 40 percent detergentselected from the group consisting of ampholytic, nonionic, cationic andanionic surfactants and mixtures thereof and from about 0.5 to 10percent of a keto acid of the formula wherein R is hydrogen or an alkylgroup having from 1 to about 20 carbon atoms and n is O to 3.

2. The composition of claim 1 wherein said keto acid is chosen from thegroup consisting of levulinic acid, glyoxylic acid and pyruvic acid andmixtures thereof.

3. The composition of claim 1 wherein said composition has a pH of fromabout 3 to about 7.

4. The composition of claim 1 wherein the surfactant is diethanolaminelauryl sulfate.

5. A detergent composition consisting essentially of from about 50 to94.5 percent water, from about 5 to about 40 percent detergent selectedfrom the group consisting of ampholytic, nonionic, cationic and anionicsurfactants and mixtures thereof and from about 0.5 to 10 perce'nt of aketo acid of the formula wherein R is hydrogen or a methyl group and nis 0 to 3.

6. The composition of claim 5, wherein said keto acid is glyoxylic acid.

7. The composition of claim 5, wherein said keto acid is pyruvic acid.

8. The composition of claim 5 wherein the keto acid is levulinic acid.

2. The composition of claim 1 wherein said keto acid is chosen from thegroup consisting of levulinic acid, glyoxylic acid and pyruvic acid andmixtures thereof.
 3. The composition of claim 1 wherein said compositionhas a pH of from about 3 to about
 7. 4. The composition of claim 1wherein the surfactant is diethanolamine lauryl sulfate.
 5. A detergentcomposition consisting essentially of from about 50 to 94.5 percentwater, from about 5 to about 40 percent detergent selected from thegroup consisting of ampholytic, nonionic, cationic and anionicsurfactants and mixtures thereof and from about 0.5 to 10 percent of aketo acid of the formula
 6. The composition of claim 5, wherein saidketo acid is glyoxylic acid.
 7. The composition of claim 5, wherein saidketo acid is pyruvic acid.
 8. The composition of claim 5 wherein theketo acid is levulinic acid.